Windies skipper Kraigg Brathwaite broke Head's heart by bowling him on 99 in the first innings of the series opener in Perth, and the 28-year-old did not get the chance to go one better in the second.
But in his sixth Test innings on his home deck, Head had the last laugh with a classy ton that confirmed Australia will head into day two with all the momentum.
The century will go some way to helping Head mount a case for selection on the tour of India that begins in February.
After losing the toss, West Indies' best bet was to try to parlay low light into wickets in the third session and leave themselves as little as possible to do on the second day.
But it was in darkness that Head and Marnus Labuschagne flourished, determined not to give up their wickets cheaply, as David Warner (21) and Steve Smith (0) had before them.
Head is the perfect No.5, able to play second fiddle just as easily as cut loose with rapid-fire runs.
His feverish approach to his work cemented his spot in the Test side after his recall last summer and was on show again on Thursday.
The South Australia captain notably slashed debutant Devon Thomas for four on consecutive deliveries.
West Indies took the second new ball as Head was approaching the nervous nineties so the 28-year-old slowed his pace.
Just as it appeared the clock could beat him, Head belted a four past deep extra cover, backing it up with another four past long off that sealed his ton.
